Kourkine Igor V., Chapman Michael B., Glueck David S., Eichele Klaus, Wasylishen Roderick E., Yap Glenn P. A., Liable-Sands Louise M., Rheingold Arnold L.
Department of Chemistry, University of Delaware, Newark, Delaware 19716.
Inorg Chem. 1996 Mar 13;35(6):1478-1485. doi: 10.1021/ic951020i.
The stable primary phosphine complexes trans-M(PH(2)Mes)(2)Cl(2) (1, M = Pd; 2, M = Pt; Mes = 2,4,6-(t-Bu)(3)C(6)H(2)) were prepared from Pd(PhCN)(2)Cl(2) and K(2)PtCl(4), respectively. Reaction of Pt(COD)Cl(2) (COD = 1,5-cyclooctadiene) with less bulky arylphosphines gives the unstable cis-Pt(PH(2)Ar)(2)Cl(2) (3, Ar = Is = 2,4,6-(i-Pr)(3)C(6)H(2); 4, Ar = Mes = 2,4,6-Me(3)C(6)H(2)). Spontaneous dehydrochlorination of 4 or direct reaction of K(2)PtCl(4) with 2 equiv of PH(2)Mes gives the insoluble primary phosphido-bridged dimer Pt(PH(2)Mes)(&mgr;-PHMes)Cl (5), which was characterized spectroscopically, including solid-state (31)P NMR studies. The reversible reaction of 5 with PH(2)Mes gives Pt(PH(2)Mes)(2)(&mgr;-PHMes)Cl (6), while PEt(3) yields Pt(PEt(3))(2)(&mgr;-PHMes)Cl (7), which on recrystallization forms Pt(PEt(3))(&mgr;-PHMes)Cl (8). Complex 5 and PPh(3) afford Pt(PPh(3))(&mgr;-PHMes)Cl (9). Addition of 1,2-bis(diphenylphosphino)ethane (dppe) to 5 gives the dicationic Pt(dppe)(&mgr;-PHMes)Cl (10-Cl), which was also obtained as the tetrafluoroborate salt 10-BF(4)() by deprotonation of [Pt(dppe)(PH(2)Mes)Cl][BF(4)] (11) with Et(3)N or by reaction of Pt(dppe)(&mgr;-OH)BF(4) with 2 equiv of PH(2)Mes. Complexes 8, 9, and 10-Cl.2CH(2)Cl(2).2H(2)O were characterized crystallographically.
